Interaction Potentials and Vibrational Effects in the Acetylene Dimer

4562

J. Phys. Chem. A 2000, 104, 4562-4570

Interaction Potentials and Vibrational Effects in the Acetylene Dimer Kimberly Shuler and Clifford E. Dykstra* Department of Chemistry, Indiana UniVersity-Purdue UniVersity Indianapolis, 402 N. Blackford Street, Indianapolis, Indiana 46202 ReceiVed: NoVember 15, 1999; In Final Form: February 28, 2000

Ab initio calculations were carried out for critical point regions of the acetylene dimer potential surface with different basis sets, with and without the inclusion of counterpoise correction, and at two different electron correlation levels. The results were used to determine parameters for model interaction potentials with different forms for their electrostatic terms. Vibrational quantum Monte Carlo calculations for rigid monomers were performed using each of the model potentials, and refinements of the few parameters in the model potentials were obtained, such that the calculated rotational constant for the ground vibrational state matched the experimentally determined value. Comparison of features of the resulting surfaces showed that similar surfaces could be obtained from the different ab initio starting points, an indication of the suitability of the potentials’ forms and of the nature of lingering errors in the ab initio treatments. This provides a very useful basis for more general model development. Specific information obtained about the acetylene dimer is that the changes in the rotational constant due to vibrational averaging are about 2% and that the dissociation energy from the ground vibrational state is about 400 cm-1.

Introduction One reason for interest in the weak interaction of acetylene with rare gas atoms and with other molecular partners is that although acetylene has no net dipole, it has hydrogens that may participate in hydrogen bonding. Generally, the interaction strength of acetylene for partner molecules or molecular clusters is small relative to those of molecules with permanent dipoles (e.g., water), and hence, acetylene provides a special probe of the complicated juxtaposition of effects that comprise noncovalent and hydrogen bonding interactions. The acetylene dimer has been the subject of a number of key experimental studies,1-11 and it is known to have a T-shaped equilibrium structure, a result verified by ab initio studies.12-18 Although the T-shaped structure is consistent with the attractive interaction of the acetylenes’ quadrupoles, the interaction is more complicated in that the quadrupole-quadrupole interaction is only a share of the total interaction strength at equilibrium. In an effort to understand the contributing effects of the acetyleneacetylene interaction at a detailed level suited to deriving elements for transferable potential parameters, a series of ab initio calculations were carried out for the acetylene dimer. These were used to locate three symmetry-constrained minima and map out limited regions of the potential surface in their vicinity. The three structures test different features of a representation (e.g., model) of the interaction surface. A further assessment of the model potentials was accomplished through the calculation of ground vibrational state properties. There have been a number of studies wherein the acetyleneacetylene interaction potential has been modeled, fitted, or otherwise represented.18-22 In many cases, this was done in the course of performing a partial dynamical analysis, sometimes for the interesting interconversion process in the acetylene dimer and/or for vibrational energies. Our primary interest in performing new ab initio calculations on the acetylene dimer was in model potential development. Relatively simple forms for the potentials of weakly interacting species can often serve to

represent key surface features, and their simplicity makes them attractive for dynamical analysis and mixed quantum mechanical-molecular mechanics approaches. More features can be represented and/or accuracy improved with increasing the complexity of the functional form of an interaction potential, and hence, one is ultimately concerned with the tradeoff between the quality of the representation and the computational cost of using it in dynamical simulations. In addition to this concern, we wish to understand, and exploit as much as possible, the transferability of potential parameters, such as the values for electrical moments and polarizabilities of the constituent monomers. These two considerations often guide the selection of potential forms used for the study of weakly bound clusters. Theoretical Approach Ab initio calculations were performed for (HCCH)2 with the monomer bond lengths fixed at values obtained by Assfeld et al.,23 RCC ) 1.2143 Å and RCH ) 1.0649 Å. The cc-pVTZ basis set of Dunning24 was used in most of the calculations, and it consisted of 176 basis functions for (HCCH)2. Certain test calculations were performed with this set, augmented with additional even-tempered uncontracted functions, one set of diffuse s functions on each center (exponents ) 0.0324 [H] and 0.0453 [C]), one set of diffuse p functions (exponents ) 0.107 [H] and 0.0382 [C]), and two sets of diffuse d functions on the carbon centers (exponents ) 0.0922 and 0.0267 [C]) for a total of 248 functions. Counterpoise correction for basis set superposition error (designated herein with “/cc”) was made with the Boys-Bernardi scheme.25 Correlation energies were evaluated at the MP2 level of treatment, with selected tests done with the double substitution coupled cluster treatment ACCD (approximate double substitution coupled cluster,26 a treatment first developed as ACP-D45 by Jankowski and Paldus.27 ACCD or ACP-D45 exploits a near cancellation in certain small Hamiltonian matrix elements in

10.1021/jp9940405 CCC: $19.00 © 2000 American Chemical Society Published on Web 04/26/2000

Weak Interaction in the Acetylene Dimer

J. Phys. Chem. A, Vol. 104, No. 19, 2000 4563 TABLE 1: Comparison of (HCCH)2 Energies at a near Equilibrium Structurea level of treatmentb

electronic energy (au)

interaction energy (cm-1)

SCF SCF/cc MP2 MP2 (SCF/cc) MP2/cc ACCD ACCD (SCF/cc) ACCD/cc

176-function basis -153.696 72 -153.696 59 -154.379 86 -154.379 74 -154.379 24 -154.392 85 -154.392 73 -154.392 27

184 157 622 595 487 518 491 391

SCF SCF/cc MP2 MP2 (SCF/cc) MP2/cc

248-function basis -153.697 66 -153.697 59 -154.385 20 -154.385 13 -154.384 43

160 146 687 673 519

a T-shaped structure with R b com ) 4.3246 Å. “/cc” designates counterpoise correction.25

Figure 1. The three structures of the acetylene dimer characterized by ab initio calculations. The planar T-shaped structure (upper left) is the global minimum. The slipped parallel structure (bottom) is a planar structure constrained in the geometry optimization to have C2h symmetry, and the crossed structure (upper right) has the monomers perpendicular, constrained to D2d symmetry.

the CCD treatment and produces property values and potential surfaces very similar to CCD.28,29 The model potentials used to represent the dimer surface followed the molecular mechanics for clusters (MMC) scheme30 in expressing the interaction as a sum of the classically evaluated electrical interaction energy plus Lennard-Jones or 6-12 terms among different monomer sites. The electrical interaction is the sum of the permanent moment interaction and polarization energy based on the dipole and quadrupole polarizabilities of the monomers, whereas the 6-12 terms are treated with adjustable parameters. Here, the adjustment of these parameters was done first to match the ab initio description of the surface in the vicinity of the T-shaped global equilibrium structure and the lowest energy crossed and slipped parallel structures (Figure 1). Different parameter sets were determined for different sets of ab initio data and with three representations of acetylene’s permanent charge field. Using each of the model potentials, vibrational analysis was carried out for (HCCH)2 via rigid body diffusion quantum Monte Carlo (RBDQMC) calculation. This treatment follows Anderson’s diffusion quantum Monte Carlo (DQMC) approach31 but with the complication that the diffusion steps must include the rotation of the rigid molecule about its principal axes in addition to the translation of the mass centers. The advantage is that for a given precision in the simulation, longer time steps can be used because the high frequency intramolecular vibrational motions are excluded via the imposition of monomer rigidity. A number of RBDQMC calculations have been reported for weakly bound clusters,32-39 and in particular, Gregory and Clary have shown good agreement of DQMC and RBDQMC for zeropoint energies and rotational constants.35 For the RBDQMC calculational results given here, the time step was 4.0 au (time)

[1.0 au (time) or 1.0 h/(2πEh) ) 2.418 88 × 10-17 s]. The number of QMC-psips was 8000, and the energy and property evaluations were performed through 126 000 time steps each. These were carried out following an equilibration sequence of at least 10 000 time steps of decreasing size and an overall duration of 6 × 105 au. The RBDQMC simulation yielded weights that reflect, but are not strictly, those of the vibrational state probability densities.40 The true probability density may be obtained by descendant weighting,41,42 and thus, rotational constants were calculated by averaging the inverses of the principal moments of inertia with these probability densities. More direct connection with spectroscopic measurement is obtainable from calculations that yield rotational excited-state energies and sets of transition energies such that rotational constants can be obtained following the same analysis applied to spectroscopic data.43,44 We expect the errors from the averaging approach to be small and comparable to other lingering error sources, such as the assumed rigidity of HCCH. Finally, a readjustment of parameters in the model potentials was performed to bring the RBDQMC values of the rotational constants in line with spectroscopic values. The changes in the surfaces from this refinement serve to characterize the lingering errors in the ab initio information and the suitability of the form of the model potential in ways discussed below. Results and Discussion Ab Initio Calculations. For the different levels of calculation that were performed, Table 1 gives the calculated electronic energies of a near equilibrium (T-shaped) structure, one of the surface points evaluated at all levels. Also given are the interaction energies, which are expressed here as energies at a given structure subtracted from the corresponding energies of two noninteracting monomers. Positive values correspond to attractive interaction. The values in Table 1 reveal first that the counterpoise correction with the cc-pVTZ (176 function) basis at the SCF level is small, 27 cm-1. Of course, SCF is insufficient to decsribe the interaction fully, and correlation effects deepen the well in this region by at least 300 cm-1. The MP2 interaction energy for the specific T-shaped structure of Table 1 is 622 cm-1. The counterpoise correction to the correlation energy of 108 cm-1 is also more than the corresponding SCF correction. The enlargement of the basis with diffuse functions (248-function set) reduces the interaction energy at the SCF level by 24 cm-1.

4564 J. Phys. Chem. A, Vol. 104, No. 19, 2000

Shuler and Dykstra

TABLE 2: Minimum Energy T-Shaped Structures of (HCCH)2 from ab Initio Calculations Rcom (Å)

(Beq+Ceq)/2 (MHz)

TABLE 3: Summary of ab Initio Calculations of the Equilibrium Interaction Energy and Separation Distance

interaction energy De (cm-1)

calculation

Rcom (Å)

interaction energy De (cm-1)

this work (MP2/cc 248 fcns.) Alberts et al.13 Bone and Handy15 Hobza et al.16 Karpfen (Basis III)17

4.358 4.311 4.344 4.493 4.31

530 577 551 441 507

MP2 MP2 (SCF/cc) MP2/cc ACCD/cc

176-function basis 4.285 1941 4.293 1934 4.381 1863 4.472 1794

595 596 490 410

MP2 MP2 (SCF/cc) MP2/cc

248-function basis 4.285 1941 4.303 1927 4.358 1882

677 678 530

Mostly, this corresponds to diminishing the lingering basis set superposition error, and consequently, the SCF interaction energy after counterpoise correction changes only slightly, from 157 to 146 cm-1. In contrast, the basis set enlargement increases both the correlation contribution to the well depth and the counterpoise correction to the correlation effect. These are offsetting changes, and hence, the MP2 interaction energy after counterpoise correction changes only 32 cm-1, from 487 to 519 cm-1. The description of the polarization and dispersion elements of the interaction are surely improved by the addition of diffuse polarization functions, and the 32 cm-1 increase in the interaction energy is in line with this description. The increase in counterpoise correction to the correlation energy is attributed to the added diffuse functions helping the correlation description of each partner, partly because of their extensiveness. Diminishment of basis set superposition effects calls for improvement of the core and valence sets of the monomers, though that does not add the flexibility for improving the description of intermolecular polarization. Thus, basis set enlargement in the diffuse regions has largely an orthogonal effect from basis set enlargement in the core and valence regions. For our purposes, it is useful to see that the 40% increase in the number of basis functions in the larger set relative to the cc-pVTZ set affected the counterpoise corrected MP2 interaction energy by only about 6%. We do not expect a significant change from further augmentation with diffuse functions, and we rely on the counterpoise correction for estimating the errors due to lingering deficiencies in the core and valence parts of the basis. Results of the ACCD calculations, included in Table 1, show the possibility of an overshoot in the correlation effects at the MP2 level. ACCD yields an interaction energy (De) diminished by 96 cm-1 after counterpoise correction. In the approach to an exact treatment, this difference from the MP2 value could be modified somewhat, including being partly offset by improvements in the basis such as with the 248-function set. A more complete comparison of the different electronic structure treatments comes from looking at other areas of the surface, not simply a single surface point. The first task to be completed was to find the global equilibrium structure with the different levels of treatment, and Table 2 presents the results obtained, including results for the equilibrium on the counterpoise corrected surfaces. Because the correlation effects and counterpoise corrections do not simply move a surface (or a surface slice) upward or downward but instead slightly change the shape of the surface, there are differences in the optimum separation distances. The counterpoise correction alone lengthens the equilibrium separation distance by 0.09 Å. A further lengthening may arise through more complete treatment of the electron correlation, as found in the ACCD results in Table 2. The sensitivity of the well-depths (stabilities at global equilibrium structures) are less than that found for the single structural point in Table 1. Thus, enlargement of the basis from 176 to

TABLE 4: Symmetry-Constrained Optimum Structuresa of (HCCH)2 from ab Initio Calculations D2h (cross)

MP2 MP2 (SCF/cc)b MP2/cc ACCD/cc

C2h (slipped parallel)

Rcom (Å)


Rcom (Å)

θ


3.922 3.995 4.096 ∞

63 64 52 0

4.220 4.242 4.288 4.477

138.1 138.1 138.0 138.3

512 513 439 349

a Obtained with the 176-function basis. b Counterpoise correction is that of the SCF level treatment only.

248 functions changes De from 490 to 530 cm-1, and using ACCD instead of MP2 for the correlation treatment changes it from 490 to 410 cm-1. Table 3 provides a comparison with prior studies of the acetylene dimer for the equilibrium structure, and there are no unusual differences. The most recent prior ab initio work is that of Karpfen,17 who has provided comparisons of MP2 results with eight different basis sets. Other areas of the surface were considered to obtain a fuller comparison of the different electronic structure treatments. We examined three other structures optimized with symmetry constraints. For the first, a collinear constraint, there was no minimum. The quadrupole-quadrupole repulsion appears sufficient to overcome the dispersion effects and preclude a shallow well, at least at the levels of treatment employed here. Symmetry constrained optimum structures were found for D2h and C2h structures, the former having the acetylenes perpendicular to each other as in a cross and the latter having them parallel but offset or slipped (Figure 1). These surface wells (with constrained symmetry) are features that in part lock in the form of the noncovalent interaction potential between two acetylenes. They were used in constructing surface representations. Table 4 gives the ab initio values obtained for these structures. The interaction energy of the slipped parallel structure is slightly less than the interaction energy at the global minimum (Tshaped). In contrast, the crossed structure is associated with a much smaller dip or well in the surface. At the ACCD level with counterpoise correction, the small dip feature was eliminated by the more complete incorporation of correlation effects, and no minimum was found for the crossed structure. Additional calculations were performed with single substitutions included in the coupled cluster treatment, but their effects were very small, amounting to a less than 0.01 Å change in optimum separation distances and less than 10 cm-1 changes in stabilities. Representations of the Potential Surface We constructed representations of the potential surfaces with a small number of adjustable parameters and choices of the form of the representation. In all of the cases, the potential for the rigid acetylenes, designating them as A and B, was the following

V ) Eelectrical +

∫i {sites on A}∫j>i{sites on B}

(

didj

12 rij

-

)

cicj 6

rij

(1)

Weak Interaction in the Acetylene Dimer TABLE 5: Types of Permanent Charge Field Representations Used in the Model Potentials

J. Phys. Chem. A, Vol. 104, No. 19, 2000 4565 TABLE 6: Model Potential Parameters (in au)

designation

description

selection

CQ BD

fixed central quadrupole (Q|| ) 1.808 au) C-H bond dipoles with adjustable placement along the bond; size fixed to reproduce the molecule’s quadrupole used in scheme CQ fixed central quadrupole 10% of the size of the quadrupole used in scheme CQ and C-H bond dipoles with adjustable placement and size chosen so that the total molecular quadrupole moment is the same as in scheme CQ

center

DQ

The adjustable parameters were the c’s and d’s in the 6-12 or Lennard-Jones term of eq 1, and the carbon and hydrogen atoms are the sites. Because of the symmetry of the acetylene monomer, this potential has only four adjustable parameters, a c- and d-parameter for carbon and for hydrogen centers. The 6-12 term is intended to represent everything apart from the classically evaluated electrical interaction between the monomers, i.e., the energy included in Eelectrical. The electrical energy was the polarization of each monomer by the permanent charge field of the partner molecule via the dipole and quadrupole polarizabilities, the values of these obtained from prior ab initio calculation,45 plus the interaction of the permanent moments. The back polarization or mutual polarization contributions were neglected after determining that in the vicinities of the three optimized structures, their contribution is not more than 9 cm-1. This small value is not representative of all weakly bound clusters; for instance, dipolar species will often exhibit greater mutual polarization energetics. The permanent charge field of acetylene for Eelectrical was represented first by two limiting forms labeled CQ and BD, as summarized in Table 5. CQ was simply a central quadrupole, it being the first nonvanishing moment of acetylene. The other limiting description, BD, was that of two C-H bond dipoles. Their magnitude was 0.7638 au, and their positions were (0.9396 Å from the molecule center. This arrangement yields an overall quadrupole moment identical to the central quadrupole moment used for the first representation. By suitable adjustment of the size of the dipoles, their placement can be essentially anywhere along the molecular axis and yield the same quadrupole. The particular placement we used was from treating the position as an additional adjustable parameter in the first set of searches for c and d parameters. Sensitivity to small changes in the position was so slight that we did not readjust the position in subsequent searches. A whole spectrum of representations involving moments through the quadrupole are possible, as well as other representations, and we elected to consider one specific form intermediate between CQ and BD. This form, DQ in Table 5, was chosen to be close to that of the bond dipoles, but included a central quadrupole whose size was set at 10% of the overall molecular quadrupole. The bond dipoles were then dimished in size so that the composite molecular quadrupole matched that of the CQ representation. For each electrical representation, CQ, BD, and DQ, a series of calculations was performed to search the parameter space of the four adjustable parameters. In each calculation with a model potential, the optimum T-shaped, crossed (D2h), and slipped parallel (C2V) structures were found. The adjustment of the four parameters was to match ab initio values in Table 4 to within certain tolerances. The ab initio results were those from the 176function basis at the MP2 and ACCD levels, with and without counterpoise correction. Hence, there were 12 model potentials and 12 sets of parameters. The tolerances corresponded to

parameter

to match ab initio minima carbon c

d

hydrogen c

d

to match experimental rotational constanta carbon

hydrogen

d

d

3703 3812 3671 3560

16.98 14.48 19.32 11.43

MP2 ACCD MP2/cc ACCD/cc

7.70 8.00 7.80 6.40

electrical scheme CQ 3490 0.80 16.0 3950 0.80 15.0 3800 0.80 20.0 4050 0.80 13.0


6.98 6.68 5.98 6.10

electrical scheme BD 2690 0.68 42.0 3000 0.68 42.0 2800 0.78 50.0 3350 0.50 36.0

2932 2943 2744 2931

45.78 41.20 49.00 31.50


6.48 5.95 6.08 5.00

electrical scheme DQ 2490 0.78 52.0 2680 0.65 52.0 2540 0.65 65.0 3025 0.80 52.0

2699 2626 2474 2632

56.37 50.96 63.31 45.24

a The c parameters were kept at the values selected from matching minima.

weighting the match for the global equilibrium as the most important and the crossed structure as the least important. After selecting an initial set of tolerances and optimizing the parameters, attempts were made to reduce the largest tolerances. The search stopped when no further improvement could be achieved. The values that remained with large tolerances help identify limitations of the form of the potential. Table 6 gives the values of the 4 parameters for the 12 model potentials, and Table 7 gives the surface features of these 12 potentials that correspond to those obtained by ab initio calculation (Table 4). The disagreement of the model potentials in reproducing Table 4 values is itemized in Table 8. Note that the crossed structure’s energy and separation distance are problematic for the CQ electrical representation with the MP2 or MP2/cc ab initio data. This problem is directly related to the attractiveness of the crossed structure at the MP2 level, an attractiveness that is mostly lost at the more complete ACCD level. At the higher correlation level, the CQ representation works about as well as the others. Refinement of the Parameters for the Potential Surfaces via DQMC Rotational constants were evaluated for each representation of the potential, both the equilibrium value and the ground vibrational state value were obtained from RBDQMC. A comparison with the experimental value of 1856.6 MHz3 showed that the model potentials were consistently yielding ground vibrational state rotational constants that were larger than the spectroscopic value. This corresponds to the molecules being found, on average, slightly too close in the DQMC simulations with the model potentials. The consistency of this difference suggests that it results from the small, lingering deficiencies in the ab initio surface data. As a means of examining this, we adjusted the nonelectrical parameters in a series of RBDQMC calculations with each representation. The adjustment or refinement was to bring the ground vibrational state rotational constant in line with the spectroscopic value. We found that the smallest change in the parameters needed for this refinement was in changing only the d parameters of carbon and hydrogen. These are the parameters used in the repulsive atom-atom R-12 term, and a small increase (Table 6), mostly in the carbon parameter, was sufficient to bring about a match with the spectroscopic values for all representations.


Shuler and Dykstra

TABLE 7: Model Potential Surface Featuresa interaction energies (cm-1) T C2h D2h

ab initio level and el scheme MP2 ACCD MP2/cc ACCD/cc

a

CQ DQ BD CQ DQ BD CQ DQ BD CQ DQ BD

600 606 606 531 508 521 524 506 504 414 422 421

500 513 520 439 419 431 445 443 430 334 330 334

2 75 125 2 38 84 2 49 70 0 12 44

T

separation distances (Å) C2h D2h

4.284 4.288 4.286 4.381 4.370 4.373 4.387 4.389 4.381 4.478 4.472 4.473

4.193 4.221 4.197 4.322 4.326 4.320 4.290 4.286 4.292 4.444 4.476 4.470

5.253 4.063 3.991 5.432 4.352 4.218 5.397 4.220 4.230 ∞ 4.889 4.566

rotational constant (MHz) (B + C)eq/2 /2 1942 1939 1940 1864 1872 1870 1858 1857 1864 1790 1795 1793

1910 1917 1922 1824 1843 1841 1826 1837 1841 1739 1753 1751

Model potentials were those in which the c and d parameters were selected to match ab initio minima.

TABLE 8: Disagreement between ab Initio and Model Values for Potential Surface Featuresa error in interaction energies (cm-1) model CQ CQ CQ CQ BD BD BD BD DQ DQ DQ DQ

MP2 ACCD MP2/cc ACCD/cc MP2 ACCD MP2/cc ACCD/cc MP2 ACCD MP2/cc ACCD/cc

error in separation distances (Å)

T

C2h

D2h

T

C2h

D2h

5 11 34 4 11 1 14 25 11 12 16 12

12 8 6 15 8 13 9 2 1 25 4 19

61 18 50

0.002 0.007 0.006 0.006 0.001 0.001 0.002 0.0 0.002 0.004 0.008 0.0002

0.027 0.005 0.002 0.033 0.023 0.007 0.0004 0.002 0.001 0.001 0.002 0.0009

1.331 0.949 1.303

62 62 18 12 16 3

0.069 0.155 0.134 0.141 0.021 0.124

a The differences are the absolute differences between values obtained from the model and values obtained from the ab initio level of treatment on which the model was determined.

Certain interesting features are revealed by the values of the parameters in Table 6. First, there is a significant change in the hydrogen parameters with all representations on going from the selection based on ab initio data without counterpoise correction to the corresponding one with counterpoise correction. There is probably a greater basis set superposition effect in the vicinity of the hydrogen centers because of proximity and possibly greater basis deficiency for hydrogen centers than for carbons. Another feature is that the d parameter for hydrogen is increased for cases in which the electrical representation uses bond dipoles instead of the central quadrupole. From examining the individual pieces in the interaction energy in eq 1 at equilibrium, we find that the total nonelectrical contribution to the energy changes from 21 cm-1 with the CQ scheme to 75 cm-1 with the BD scheme. To this extent, the nonelectrical representation can compensate for deficiencies and/or different choices in the electrical part. The rotational constants at equilibrium with the 12 model potentials after refinement via the DQMC calculations (Table 9) are very similar. Their average differs from the DQMC value (i.e., the experimental value) by 1.6%. This difference is likely a good evaluation of the overall extent of the effect of vibrational averaging on /2 in the acetylene dimer. Table 9 gives surface features obtained with the various sets of model potentials. A key result is that upon refinement via RBDQMC, the surface features are very similar, regardless of the level of ab initio treatment used to construct the surface and only slightly more dependent on the electrical representation. Because the DQMC refinement that brings about this similarity

was a change in the model d parameters, the differences between surfaces using the same electrical representation are mostly in the “size” of the molecules, with the different sizes associated with different deficiencies in the ab initio treatments. However, among electrical representations, there is an important difference in the interaction energy of the crossed form. The use of bond dipoles (BD) instead of a central quadrupole (CQ) yields significantly more attractiveness for the crossed structure. This can be offset, in part, by the parameter selection for the nonelectrical part of the potential, and so, the differences among the potentials with different electrical representations are not striking. The simplest representation, CQ, proves sufficient, particularly by not exaggerating attractiveness in the crossed structure. Table 10 compares the electrical and nonelectrical interactions with the various models for the T-shaped structure. It should be noted that the nonelectrical term in eq 1 consists of two sums, one attractive and one repulsive. The entire term ends up making a small contribution in the vicinity of the equilibrium, but the individual sums are comparable in size to the electrical interaction energy. The electrical interaction is important but no more dominant in the model than the 1/R6 or 1/R12 nonelectrical terms. The different permanent charge field representations result in only small differences in the net electrical interaction. It is not surprising that these differences are, to a large extent, offset by the nonelectrical terms. We also note that the T-equilibrium interaction energies from the refined model potentials (Table 9) range from 517 to 552 cm-1 for models using the MP2/cc ab initio data and from 501 to 503 cm-1 using ACCD/cc ab initio data. A good portion, although not all, of the energy difference of MP2 versus ACCD is erased through the parameter refinement. At the same time, the remaining difference highlights to what extent reproducing the vibrationally averaged rotational constants with a model surface ensures an accurate value for the well depth. Clearly, well-depth variation of around 50 cm-1 may go along with little difference in the rotational constants. Vibrational Effects The refinement of the model surfaces and their near “convergence” from different starting points makes it meaningful to examine the vibrational averaging effects on the rotational constants and the zero point energy. As already indicated, vibrational averaging affects the value of (B + C)/2 for (HCCH)2 by about 1.6%. Table 11 gives the values for the individual constants, A, B, and C. The averaging effects on the components amount to about 2% for B and C and slightly more than 2% for A. The values in Table 11 also show that the final calculated


J. Phys. Chem. A, Vol. 104, No. 19, 2000 4567

TABLE 9: Model Potential Surface Features after RBDQMC Parameter Refinementa interaction energies (cm-1) electrical scheme CQ MP2 ACCD MP2/cc ACCD/cc electrical scheme BD MP2 ACCD MP2/cc ACCD/cc electrical scheme DQ MP2 ACCD MP2/cc ACCD/cc a

separation distances (Å)

rotational constant (MHz)

T

C2h

D2h

(B + C)eq/2

/2

1 4 2 0

4.347 4.341 4.351 4.333

4.264 4.279 4.249 4.289

5.426 5.230 5.299 ∞

1890 1895 1888 1901

1856 1857 1857 1856

462 442 442 399

103 88 73 61

4.363 4.356 4.363 4.345

4.284 4.300 4.271 4.330

4.128 4.187 4.196 4.312

1878 1883 1878 1892

1856 1856 1856 1856

460 430 457 395

61 41 52 18

4.358 4.352 4.367 4.344

4.299 4.306 4.261 4.338

4.207 4.314 4.179 4.596

1882 1886 1875 1893

1856 1856 1856 1856

T

C2h

D2h

548 561 552 503

457 459 469 404

542 534 517 501 547 521 520 503

Model d parameters adjusted to match experimental /2:

TABLE 10: Contributions to the Interaction Energy with the Model Potentialsa model:

energetic contributions (cm-1)

[eq 1] to the interaction energy

elect scheme

at a common structurea

at the optimum structuresb

ab initio basis CQ

BD

DQ

a

MP2 ACCD MP2/cc ACCD/cc MP2 ACCD MP2/cc ACCD/cc MP2 ACCD MP2/cc ACCD/cc

electrical 589 589 589 589 619 619 619 619 630 630 630 630

non-electrical original

DQMC-refined

8 -63 -70 -202 -15 -101 -99 -225 -26 -125 -131 -237

-42 -29 -38 -87 -79 -86 -103 -119 -85 -110 -111 -128

electrical

non-electrical DQMC-refined

573 577 570 583 589 595 589 593 603 608 598 615

-25 -16 -18 -80 -47 -61 -72 -92 -56 -87 -76 -112

T-shaped structure with Rcom ) 4.3246 Å. b T-shaped structure with Rcom at the optimum value for the given model potential.

values are about 10 MHz below experiment3 for B and about 10 MHz greater for C. The zero point energy is remarkably uniform, and its average for the 12 model potentials (Table 11) is 130 cm-1. We expect this to be a particularly accurate determination because of its insensitivity to the model potential. Combining this with the large basis ab initio result for De (Table 3) yields a value of 400 cm-1 for D0. This happens to match an experimental determination based on infrared intensity measurements.6 Also, it is within 4 cm-1 of an ab initio value, although in that case, De was more sizable and offset by a larger zero point energy of 173 cm-1.13 Of course, our evaluation of the zero point and dissociation energies is for the intermolecular or weak vibrational modes only because HCCH is rigid in the DQMC treatment. Laboratory measurement of D0 will include the effects of changes in intramolecular modes and will tend to be slightly different. As a further assessment of the potential and of vibrational features, DQMC calculations were performed for all deuterated forms of the dimer, i.e., those with one, two, three, or four deuterium atoms in place of hydrogens. The potential was the CQ-ACCD/cc model potential, and for these calculations, the number of psips was increased from 8000 to 10 000. The results are given in Table 12. For (HCCH)2, the change in the number of psips affected the value of /2 by less than 1 MHz. The rotational constants for the deuterated species have been obtained spectroscopically.7 With one deuterium, one structure

was observed,7 and in our DQMC calculations, those that were biased with different initial starting structures yielded indistinguishable sets of rotational constants and energies. That is, the calculations yielded one state that we associate with the structure observed. It has the single deuterium in the “bonding” position, which would be the position expected to exhibit the most sizable diminishment in zero point energy from deuteration and, thus, the most stable structure. Comparison with the calculated values (Table 12) shows that the /2 values agree with experimental to 2.7 MHz, or about 0.1%. Furthermore, the small differences for the individual values of A, B, and C are in the same direction and of roughly the same sizes as the differences found for (HCCH)2. With two deuteriums in the dimer, spectroscopic measurement7 has found two forms, one with each monomer having a deuterium and the other being the DCCD-HCCH complex. Our DQMC calculations yielded only two distinguishable forms, and their < B + C>/2 rotational constants (Table 12) are within 2 MHz of the measured values. With three deuteriums, we obtain rotational constants that match one of the two structures reported.7 We do not obtain rotational constants consistent with any other structure. Thus, we do not obtain the one designated D1,7 which has HCCD pointing to the middle of DCCD. However, the DQMC treatment normally selects the vibrational ground state, making excited vibrational states inaccessible. A second conformer of the same molecules, HCCD and DCCD,


Shuler and Dykstra

TABLE 11: Vibrational Ground State Features model:

rotational constants (MHz)

elect scheme/ ab initio basis CQ


BD


DQ


Expt 3

interaction energy

zero point energy (cm-1)

-1

Aeq

Beq

Ceq

De (cm )

〈A〉

〈B〉

〈C〉

D0 (cm-1)

34 895 33 720 34 895 33 820 34 895 33 660 34 895 33 810 34 896 34 140 34 896 34 190 34 896 34 140 34 896 34 240 34 896 34 340 34 896 34 370 34 896 34 320 34 896 34 430 35 188

1941 1905 1946 1906 1939 1906 1953 1905 1928 1904 1934 1904 1928 1904 1943 1906 1937 1904 1937 1891 1925 1904 1944 1904 1914.3

1839 1807 1844 1808 1837 1807 1850 1807 1827 1807 1833 1807 1827 1807 1840 1807 1836 1807 1836 1796 1824 1808 1842 1808 1798.8

548 417 561 427 552 423 503 372 542 415 534 405 517 391 501 372 521 416 521 391 520 396 503 370

131 134 129 131 127 129 126 126 131 130 124 133

TABLE 12: Vibrational Ground State Features of Deuterated Dimers clustera HCCH-HCCH DQMCb Expt3 HCCD-HCCH DQMCb Expt-A27 DCCD-HCCH DQMCb Expt-B27 HCCD-HCCD DQMCb Expt-C27 DCCD-DCCH DQMCb Expt-D37 DCCD-DCCD DQMCb Expt-E7

〈A〉

rotational constants (MHz) 〈B〉 〈C〉

/2

interaction energy D0 (cm-1)

zero point energy (cm-1)

33 820 35 188

1904 1914.3

1806 1798.8

1855 1856.6

372

131

33 590 35 768

1901 1911.3

1803 1798.0

1852 1854.7

377

126

32 500 35 631

1809 1811.1

1716 1709.1

1762 1760.1

379

124

28 530 30 326

1870 1879.6

1758 1752.0

1814 1815.8

380

123

24 600 26 007

1839 1849.4

1714 1707.9

1776 1778.7

383

120

24 500 26 026

1745 1752.0

1632 1624.3

1689 1688.2

386

117

a The clusters are specified such that the left monomer points into the middle right monomer and the D or H to the left of the hyphen is the center hydrogen bonding center (Figure 1). The experimental results from ref 7 are given with the identifiers used in that report to the different forms (e.g., A2, D3, etc.). b The model potential was that of the CQ representation derived from ACCD/cc ab initio results with DQMC refinement of parameters.

corresponds to an excited state on the whole of the global interaction potential. The results in Table 12 demonstrate that the reliability of the model potential for ground vibrational state rotational constants shows little sensitivity to substitution of one to four deuterium atoms. That is a good indication of the accuracy of the potential for the regions of the surface sampled in the course of ground vibrational state excursions. The accuracy of the potential in other regions may be worse, but one interesting assessment of that is shown in Figure 2. Model and ab initio calculations were performed to follow the minimum energy path away from the C2h interconversion transition state (a planar structure) as the monomers were twisted out of plane in a concerted fashion that preserves C2 symmetry (i.e., preserves

equivalence of the monomers). The model and ab initio results are not sharply different, and both show a very shallow potential surface slice. There is good agreement in the shaping of the surfaces in this nonequilibrium region. There is, however, a difference in their C2h energies, which serve to reference the energies in Figure 2. The C2h energies are the interconversion barrier heights, and the ab initio ACCD/cc value is 61 cm-1 (Tables 2 and 4), whereas the model value after DQMC refinement is 99 cm-1 (Table 9, CQ:ACCD/cc). Whether the lingering error in the ab initio calculations or model error is responsible for the difference cannot be determined on the basis of the calculations alone. Experimental information on the interconversion tunneling frequency is available,3,4,7 and low-dimensional dynamical


Figure 2. Minimum energy path for the concerted out-of-plane twisting of the acetylenes from the C2h (slipped parallel) transition state structure for the interconversion. The horizontal axis gives the magnitude of the out-of-plane angle for each acetylene, the two molecules being twisted in an opposed sense with C2 symmetry preserved. The energy in cm-1 relative to the optimum C2h structure’s energy is the vertical axis. The broken line is that obtained using the model potential of the CQ representation derived from ACCD/cc ab initio results with DQMC refinement of parameters. The solid line is from ab initio MP2/cc calculations with the 176-function basis.

analyses with that information imply barriers of 33.2 cm-1 and 35.6 cm-1.3,7 These are less than our ab initio ACCD/cc value of 61 cm-1 and less than other large basis ab initio values such as 59 cm-1 and 76 cm-1.13,11 This may suggest that the true barrier is overvalued even with fairly extensive levels of ab initio treatment, and also, that our model with its still higher barrier is worse. On the other hand, the surface slice in Figure 2 suggests the likelihood for very complicated interconversion dynamics in a way that could make a one-dimensional analysis (to match a measured tunneling frequency) undershoot the true barrier height. Figure 2 shows the variation of the interaction energy with out-of-plane distortion with the acetylenes remaining equivalent in structure. Their equivalence means that each point on the curve in Figure 2 is a structure that is halfway on a path from one T-shape or its interconversion partner T-shape. The potential energy rises quite slowly with the torsional angle, and this means that the interconversion can take place through a range of nonplanar vibrational excursions with about the same energetic ease as through the planar transition state. Hence, a planar treatment of tunneling will necessarily yield less likelihood for interconversion, and in turn, the planar barrier needed to match a measured tunneling splitting will be diminished. We have not sought to concretely establish the barrier height, but the consistency of our calculations, and others done with large basis sets, does not support values for the barrier less than 50 cm-1. With that, the new surface feature revealed in Figure 2 may indicate complexity in the interconversion process that plays a role in the difference. Conclusions Ab initio calculations for structures of (HCCH)2 gave energetics and separation distances that were represented by model potentials with three choices for representing acetylene’s permanent charge field. The simplest choice, a central quadrupole representation, seemed about as sufficient as the somewhat more complicated distributed forms for this particular dimer. More interesting is that model potentials that were similar in parameter values, surface features, and sizes of energetic elements were obtained for a given electrical representation upon refinement of the repulsive parameters (the d’s) so as to match the spectroscopically measured value of (B + C)/2 for (HCCH)2.

J. Phys. Chem. A, Vol. 104, No. 19, 2000 4569 This is a sort of convergence in models that points to the suitability of the form of the functions in the model potential for describing the system in its ground vibrational state. That this form is simple and designed for transferability is important for a larger class of possible applications of the model. It also shows that at the threshold of a large basis set with correlation included, the small lingering errors in ab initio calculations tend to be in the effective sizes of the monomers, a feature we have seen for Ar-H2S and Ne-H2S.46 Hence, calculations at simple levels such as MP2 might prove more reliable for similar weakly bound clusters with small, rather easily made adjustments of this sort. The convergence in the models makes it likely that particularly accurate values for the zero point energy and the zero point dissociation energies have been obtained. These are 130 cm-1 and 400 cm-1, respectively. We find the vibrational averaging effect on (B + C)/2 to be about 1.6%. Acknowledgment. This work was supported, in part, by a grant from the Physical Chemistry Program of the National Science Foundation (Grant No. CHE-9714016). References and Notes (1) Miller, R. E.; Vohralik, P. F.; Watts, R. O. J. Chem. Phys. 1984, 80, 5453. (2) Prichard, D. G.; Nandi, R. N.; Muenter, J. S. J. Chem. Phys. 1988, 89, 115. (3) Fraser, G. T.; Suenram, R. D.; Lovas, F. J.; Pine, A. S.; Hougen, J. T.; Lafferty, W. J.; Muenter, J. S. J. Chem. Phys. 1988, 89, 6028. (4) Ohshima, Y.; Matsumoto, Y.; Takami, M.; Kuchitsu, K. Chem. Phys. Lett. 1988, 147, 1. (5) Bryant, G. W.; Eggers, D. F.; Watts, R. O. J. Chem. Soc., Faraday Trans. 2 1988, 84, 1443. (6) Colussi, A. J.; Sander, S. P.; Friedl, R. R. Chem. Phys. Lett. 1991, 178, 497. (7) Matsumura, K.; Lovas, F. J.; Suenram, R. D. J. Mol. Spectrosc. 1991, 150, 576. (8) Bhattacharjee, R. L.; Muenter, J. S.; Coudert, L. H. J. Chem. Phys. 1992, 97, 8850. (9) Booze, J. A.; Baer, T. J. Chem. Phys. 1993, 98, 186. (10) Zhu, Y. F.; Allman, S. L.; Phillips, R. C.; Garrett, W. R.; Chen, C. H., Chem. Phys. Lett. 1994, 224, 7. (11) Buck, U.; Ettischer, I.; Schulz, S. Z. Phys. Chemie 1995, 188, 91. (12) Aoyama, T.; Matsuoka, O.; Nakagawa, N. Chem. Phys. Lett. 1979, 67, 508. (13) Alberts, I. L.; Rowlands, T. W.; Handy, N. C. J. Chem. Phys. 1988, 88, 3811. (14) Petrusova, H.; Havlas, Z.; Hobza, P.; Zahradnik, R. Collect. Czech. Chem. Commun. 1988, 53, 2495. (15) Bone, R. G. A.; Handy, N. C. Theor. Chim. Acta 1990, 78, 133. (16) Hobza, P.; Selzle, H. L.; Schlag, E. W. Collect. Czech. Chem. Commun. 1992, 57, 1186. (17) Karpfen, A. J. Phys. Chem. A 1999, 103, 11 431. (18) Resende, S. M.; De Almeida, W. B. Chem. Phys. 1996, 206, 1. (19) Fraser, G. T. J. Chem. Phys. 1989, 90, 2097. (20) Dykstra, C. E. J. Am. Chem. Soc. 1990, 112, 7540. (21) Muenter, J. S., J. Chem. Phys. 1991, 94, 2781. (22) Suni, I. I.; Klemperer, W. J. Chem. Phys. 1993, 98, 988. (23) Assfeld, X.; Almlo¨f, J. E.; Truhlar, D. G. Chem. Phys. Lett. 1995, 241, 438. (24) Dunning, T. H. J. Chem. Phys. 1989, 90, 1007. (25) Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. (26) Chiles, R. A.; Dykstra, C. E. Chem. Phys. Lett. 1981, 80, 69. (27) Jankowski, K.; Paldus, J. Int. J. Quantum Chem. 1980, 18, 1243. (28) Dykstra, C. E.; Liu, S.-Y.; Daskalakis, M. F.; Lucia, J. P.; Takahashi, M. Chem. Phys. Lett. 1987, 137, 266. (29) Dykstra, C. E.; Davidson, E. R. Int. J. Quantum Chem., submitted for publication. (30) Dykstra, C. E. J. Am. Chem. Soc. 1989, 111, 6168. (31) Anderson, J. B. J. Chem. Phys. 1975, 63, 1499. (32) Buch, V. J. Chem. Phys. 1992, 97, 726. (33) Franken, K. A.; Dykstra, C. E. J. Chem. Phys. 1994, 100, 2865. Franken, K. A.; Dykstra, C. E. Chem. Phys. Lett. 1994, 200, 161. (34) Sandler, P.; Jung, J. O.; Szczesniak, M. M.; Buch, V. J. Chem. Phys. 1994, 101, 1378. (35) Gregory, J. K.; Clary, D. C. Chem. Phys. Lett. 1994, 228, 547.

4570 J. Phys. Chem. A, Vol. 104, No. 19, 2000 (36) Gregory, J. K.; Clary, D. C. J. Chem. Phys. 1995, 102, 7817. (37) Sandler, P.; Buch, V.; Sadlej, A. J. J. Chem. Phys. 1996, 105, 10 387. (38) Niyaz, P.; Bacic, Z.; Moskowitz, J. W.; Schmidt, K. E. Chem. Phys. Lett. 1996, 252, 23. (39) Dykstra, C. E. J. Chem. Phys. 1998, 108, 6619. (40) Reynolds, P. J. J. Chem. Phys. 1990, 92, 2118. (41) Coker, D. F.; Watts, R. O. J. Phys. Chem. 1987, 91, 2513.

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Interaction Potentials and Vibrational Effects in the Acetylene Dimer

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